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United States Patent |
5,194,598
|
Hamprecht
|
March 16, 1993
|
Azo dyestuffs in which the coupling component contains an N,N-bis(alkoxy
carbonylalkyl) substituent
Abstract
Azo dyestuffs of the formula
##STR1##
in which X denotes H, F, Cl, Br, I, R, CO.sub.2 R, CN, CF.sub.3 and the
like,
Y/Z denotes H, CH.sub.3, Cl or Br,
R.sup.1, R.sup.2 and R denote C.sub.1 -C.sub.4 -alkyl and
R.sup.3 and R.sup.4 denote H or CH.sub.3, are highly suitable for the
dyeing of polyester fibres, where they are distinguished by a high
thermomigration fastness.
The preparation of the dyestuffs is preferably carried out by so-called
"halogen/cyano exchange".
Inventors:
|
Hamprecht; Rainer (Odenthal-Blecher, DE)
|
Assignee:
|
Bayer Aktiengesellschaft (Leverkusen, DE)
|
Appl. No.:
|
657617 |
Filed:
|
February 20, 1991 |
Foreign Application Priority Data
Current U.S. Class: |
534/852; 534/582; 534/597; 534/851 |
Intern'l Class: |
C09B 029/085; D06P 001/18 |
Field of Search: |
534/851,852
|
References Cited
U.S. Patent Documents
3962209 | Jun., 1976 | Gotteschlich et al. | 534/852.
|
3968099 | Jul., 1976 | Leverenz | 534/852.
|
4105655 | Aug., 1978 | Gottschlich et al. | 534/852.
|
4259237 | Mar., 1981 | Hamprecht | 534/851.
|
Foreign Patent Documents |
2759103 | Jul., 1979 | DE | 534/851.
|
2916137 | Oct., 1980 | DE | 534/852.
|
3003012 | Jul., 1981 | DE | 534/851.
|
2300784 | Sep., 1976 | FR | 534/852.
|
2305470 | Oct., 1976 | FR | 534/852.
|
2413442 | Jul., 1979 | FR | 534/851.
|
58-157863 | Sep., 1983 | JP | 534/851.
|
58-210962 | Dec., 1983 | JP | 534/852.
|
1479835 | Jul., 1977 | GB | 534/852.
|
1518290 | Jul., 1978 | GB | 534/852.
|
2034736 | Jun., 1980 | GB | 534/597.
|
Other References
ISO Recommendation R105 "Tests for Color Fastness of Textiles" (May 1959).
|
Primary Examiner: Lee; Mary C.
Assistant Examiner: Powers; Fiona T.
Attorney, Agent or Firm: Sprung Horn Kramer & Woods
Parent Case Text
This application is a continuation of application Ser. No. 256,826, filed
Oct. 12, 1988, now abandoned.
Claims
We claim:
1. An azo dyestuff of the formula
##STR19##
wherein X denotes Cl, Br or CO.sub.2 R,
R denotes C.sub.1-4 -alkyl or C.sub.5-6 cycloalkyl,
Y denotes H,
Z denotes H,
R.sup.1 /R.sup.2 denotes CH.sub.3 or C.sub.2 H.sub.5 and
R.sup.3 /R.sup.4 denotes H.
2. An azo dyestuff according to claim 1 of the formula
##STR20##
Description
The invention relates to azo dyestuffs of the formula
##STR2##
which are virtually insoluble in water and in which, independently of one
another
X denotes H, F, Cl, Br, I, R, CO.sub.2 R, COR', CN or CF.sub.3,
Y denotes H, CH.sub.3, Cl or Br,
Z denotes H, CH.sub.3, Cl or Br,
R denotes C.sub.1 -C.sub.4 -alkyl or C.sub.5 -C.sub.6 -cycloalkyl,
R' denotes R or phenyl which is unsubstituted or substituted by C.sub.1
-C.sub.4 -alkyl or Cl,
R.sup.1 /R.sup.2 denotes C.sub.1 -C.sub.4 -alkyl which is unsubstituted or
substituted by OH or C.sub.1 -C.sub.4 -alkoxy and
R.sup.3 /R.sup.4 denotes H or CH.sub.3.
Preference is given to those dyestuffs of the formula I in which
X denotes Cl, Br or CO.sub.2 R,
Y denotes H or Cl,
Z denotes H or Cl,
R.sup.1 /R.sup.2 denotes CH.sub.3 or C.sub.2 H.sub.5 and
R.sup.3 /R.sup.4 denotes H.
Among these, preference is again given to those of the formula mentioned in
which X denotes CO.sub.2 R and in particular Cl and above all Br.
Preparation of the dyestuffs is carried out by conventional methods.
A process is characterized in that anilines of the formula
##STR3##
are diazotized and coupled onto coupling components of the formula
##STR4##
The diazotization is carried out in a conventional manner at -20.degree. to
20.degree. C. by means of alkali metal nitrites, nitrosylsulphuric acid or
esters of nitrous acid in mineral acids (HCl, H.sub.2 SO.sub.4, H.sub.3
SO.sub.3) or lower fatty acids (acetic and/or propionic acid). The
coupling is also carried out by conventional methods, preferably by adding
the aqueous solution or dispersion or aqueous/alcoholic solution to the
diazonium salt solution and, if necessary, by neutralizing the reaction
mixture to a pH of 5-7 by the addition of alkali.
The preferred variation of the preparation is characterized in that the
halogen atoms of azo compounds prepared by processes known per se of the
formula
##STR5##
in which Hal denotes halogen, preferably Cl or Br, are exchanged for cyano
groups.
This exchange reaction is also known per se and described for example in
the following patent literature:
DE-A 1,544,563=GB 1,125,683
DE-A 2,456,495=GB 1,479,085
DE-A 2,759 103=GB 2,012,799
DE-A 2,846,439=GB 2,034,736
DD 217,232 (in particular the literature cited therein).
Accordingly, the o,o'-dihaloazo compound is reacted in a polar organic
solvent or water with metal cyanides or cyanide ion donors at temperatures
from 50.degree.-150.degree. C. until the halogen atoms are virtually
completely exchanged, which can easily be monitored by means of thin-layer
chromatograms.
Suitable cyanides are in particular CuCN and Zn(CN).sub.2 and also complex
cyanides of the formula Me.sup..sym..sub.n (CuCN).sub.n+1 (Me=Na, K;
n=1-3). Suitable cyanide ion-forming systems, are, for example,
formaldoxime, cyanohydrins, nitroalkanes or formamide.
Preferred organic solvents are polar aprotic compounds such as, for
example, DMF, DMSO, pyridine, N-methylpyrrolidone, chlorobenzene,
dichlorobenzenes and the like.
The halogen/cyano exchange by means of a mixture of copper(I) cyanide and
zinc cyanide is particularly suitable and preferred.
Whereas the diazo components are generally known, the coupling components
are known only in part, for example JA 47-25,488 (1972).
However, these compounds are easily obtained in a manner known per se, for
example by alkylating m-aminophenol.
Suitable coupling components are shown in the examples which follow.
The azo dyestuffs according to the invention are preferably suitable for
dyeing synthetic textile materials in particular textile materials made of
secondary cellulose acetate and cellulose triacetate, polyamide such as,
for example, polyhexamethyleneadipamide and, very particularly, of
aromatic polyester such as, for example, polyethylene terephthalate by the
dyeing methods customary for these types of fibre, using aqueous or
non-aqueous liquors.
Finally, the dyestuffs can also be applied to synthetic textile materials
by transfer printing.
Furthermore, the dyestuffs are suitable for thermal transfer printing in
optical recording processes.
The scarlet to ruby dyeings on polyester obtained by the novel dyestuffs
are distinguished by a high tinctorial strength, bright shade, and, in
particular, by a very high thermomigration fastness in combination with
good general fastness properties.
With respect to the known dyestuffs according to DE-A 2,759,103, which are
the nearest comparison, the novel dyestuffs have advantages in terms of
affinity, tinctorial strength and thermomigration fastness.
EXAMPLE 1
Preparation of the Dyestuff of the Formula
##STR6##
14.3 g of 2,4,6-tribromoaniline are dissolved in 15 ml of propionic acid
and 30 ml of glacial acetic acid and admixed at 0.degree. C. with 7.5 ml
of 42% strength nitrosylsulphuric acid over a period of 30 minutes. To
complete the diazotization, the mixture is stirred for another hour at
0.degree. C. At 0.degree.-5.degree. C., the diazotization solution is
added to a solution of 13 g of
3-hydroxy-N,N-bis(methoxycarbonylethyl)aniline in 100 ml of glacial acetic
acid and 20 ml of 10% strength aqueous amidosulphonic acid solution. The
volume is made up to 800 ml with ice water, and the mixture is stirred for
another 12 hours at 5.degree. C. The product is filtered off with suction
and washed acid-free with water. Yield: 25.7 g of an orange powder.
To 20.5 g of the tribromo dyestuff obtained in 30 ml of dimethylformamide
are added 0.54 g of copper(I) cyanide and 3.2 g of zinc cyanide, and the
mixture is stirred at 100.degree. C. for one hour. After cooling to
60.degree. C., 50 ml of methanol are added, the mixture is cooled to room
temperature, the product is filtered off with suction and washed with
dilute hydrochloric acid and water. This gives 11.1 g of the dicyanoazo
dyestuff of the above formula, which dyes polyester in a bright yellowish
red having a very good thermomigration fastness.
By an analogous or similar method, the dyestuffs listed in the table which
follows can be obtained in good yields.
__________________________________________________________________________
Example Shade on
No. Formula polyester
__________________________________________________________________________
##STR7## yellowish red
3
##STR8## yellowish red
4
##STR9## yellowish red
5
##STR10## yellowish red
6
##STR11## red
7
##STR12## red
8
##STR13## red
9
##STR14## red
10
##STR15## bluish red
11
##STR16## yellowish red
12
##STR17## yellowish
__________________________________________________________________________
red
EXAMPLE 13
Preparation of the Dyestuff of the Formula
##STR18##
6.64 g of ethyl 2-methyl-3,5-dicyano-4-aminobenzoate (preparation according
to EP 95,638) are dissolved in 20 ml of propionic acid and 40 ml of
glacial acetic acid and admixed at 0.degree. C. with 5 ml of 42% strength
nitrosylsulphuric acid with stirring over a period of 30 minutes. Stirring
is continued for 90 minutes at 0.degree. C., and a solution of 8.6 g of
3-hydroxy-N,N-bis-(methoxycarbonylethyl)aniline in 50 ml of methanol are
then added to the diazotization solution. The volume is made up to 600 ml
with ice water. Stirring is continued for 15 hours, the product is
filtered off with suction and washed neutral with water. The dyestuff
obtained dyes polyester in a bluish red having good fastness properties.
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